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CHFClI |
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Chlorine and Iodine |
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Nuclear
Quadrupole Coupling Constants |
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in Chlorofluoroiodomethane
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Full iodine and chlorine nqcc tensors in chlorofluoroiodomethane, as well as several ab initio molecular structures, were determined by Cuisset et al. [1]. |
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Calculation of the nqcc tensors was made here on the MP2/SDB-VTZ and on the ab initio re structures (see ref [1]). These nqcc's are compared with the
experimental values in Tables 1 - 3. Structure parameters are
given in Table 4. |
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In Tables 1 - 3, subscripts a,b,c refer to the principal axes of the inertia
tensor; x,y,z to the principal axes of the nqcc tensor. Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root mean
square
difference between calculated and experimental diagonal nqcc's
(percentage of the average of the magnitudes of the experimental
nqcc's). RSD is the calibration residual standard deviation of
the models for calculation of the nqcc's: For iodine,
B1LYP/6-311G(df,p); and for chlorine, B1LYP/TZV(3df,2p).
Ahlrichs' TZV basis for iodine is available here. |
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Table 1. Chlorine nqcc's in CHFClI (MHz). Calc. = B1LYP/TZV(3df,2p). |
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Calc (1) was made on the MP2/SDB-VTZ structure. |
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Calc (2) was made on the ab initio equilibrium structure. |
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Calc (1) |
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Calc (2) |
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Expt. [1] |
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Xaa(35Cl) |
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14.13 |
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14.14 |
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13.3970(34) |
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Xbb |
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15.52 |
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15.43 |
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15.4498 |
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Xcc |
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29.64 |
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29.56 |
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28.8468(38) |
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|Xab| |
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51.98 * |
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51.99 * |
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51.3943(117) * |
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|Xac| |
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22.32 |
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22.36 |
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22.7366(201) |
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|Xbc| |
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20.54 |
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20.63 |
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21.107(40) |
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RMS |
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0.62 (3.2 %) |
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0.60 (3.1 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xxx |
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36.24 |
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36.31 |
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36.025(35) |
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Xyy |
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39.30 |
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39.25 |
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39.045(25) |
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Xzz |
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75.53 |
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75.56 |
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75.070(22) |
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ETA |
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0.0405 |
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0.0390 |
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0.04023(65) |
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Øz,CCl |
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1.77 |
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1.81 |
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Xaa(37Cl) |
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12.18 |
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12.18 |
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11.5924(59) |
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Xbb |
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11.25 |
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11.18 |
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11.2132 |
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Xcc |
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23.43 |
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23.37 |
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22.8056(67) |
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|Xab| |
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41.00 * |
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41.01 * |
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40.5472(139) * |
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|Xac| |
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17.71 |
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17.74 |
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18.0474(234) |
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|Xbc| |
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15.89 |
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15.96 |
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16.343(46) |
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RMS |
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0.49 (3.2 %) |
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0.47 (3.1 %) |
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RSD |
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0.44 (1.1 %) |
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0.44 (1.1 %) |
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* The algebraic sign of the product XabXacXbc is negative. |
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Table 2. 127I nqcc's in CHF35ClI (MHz). Calc. = B1LYP/6-311G(df,p). |
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Calc (1) was made on the MP2/SDB-VTZ structure. |
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Calc (2) was made on the ab initio equilibrium structure. |
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Calc (1) |
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Calc (2) |
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Expt. [1] |
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Xaa |
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1711.0 |
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1707.6 |
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1704.58015(252) |
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Xbb |
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836.8 |
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835.1 |
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838.57959 |
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Xcc |
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874.2 |
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872.5 |
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866.00056(244) |
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|Xab| |
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695.6 * |
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698.9 * |
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699.7668(61) * |
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|Xac| |
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602.2 |
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605.4 |
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622.6878(160) |
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|Xbc| |
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134.2 |
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136.4 |
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140.4346(265) |
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RMS |
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6.1 (0.54 %) |
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4.6 (0.40 %) |
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RSD |
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15.2 (1.23 %) |
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15.2 (1.23 %) |
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Xxx |
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991.0 |
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991.4 |
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993.177(27) |
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Xyy |
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1029.0 |
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1028.6 |
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1032.013(25) |
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Xzz |
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2020.0 |
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2020.1 |
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2025.218(9) |
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ETA |
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0.0188 |
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0.0184 |
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0.01918(2) |
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Øz,Cl |
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0.91 |
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0.92 |
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* The algebraic sign of the product XabXacXbc is negative. |
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Table 3. 127I nqcc's in CHF37ClI (MHz). Calc. = B1LYP/6-311G(df,p). |
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Calc (1) was made on the MP2/SDB-VTZ structure. |
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Calc (2) was made on the ab initio equilibrium structure. |
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Calc (1) |
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Calc (2) |
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Expt. [1] |
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Xaa |
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1692.4 |
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1688.9 |
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1685.7418(42) |
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Xbb |
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818.8 |
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817.1 |
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820.3798 |
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Xcc |
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873.6 |
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871.9 |
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865.3620(47) |
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|Xab| |
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727.7 * |
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730.1 * |
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731.8297(68) * |
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|Xac| |
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601.6 |
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604.8 |
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622.004(132) |
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|Xbc| |
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142.2 |
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144.4 |
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148.7207(247) |
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RMS |
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6.2 (0.55 %) |
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4.6 (0.41 %) |
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RSD |
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15.2 (1.23 %) |
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15.2 (1.23 %) |
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Xxx |
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991.0 |
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991.4 |
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993.200(25) |
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Xyy |
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1029.0 |
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1028.6 |
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1031.977(23) |
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Xzz |
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2020.0 |
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2020.1 |
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2025.177(8) |
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ETA |
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0.0188 |
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0.0184 |
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0.01915(2) |
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Øz,Cl |
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0.91 |
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0.92 |
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* The algebraic sign of the product XabXacXbc is negative. |
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| Table 4. CHFClI. Molecular structure parameters, MP2/SDB-VTZ and ab initio re [1] (Å and degrees). The structures are given here in Z-matrix format. |
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MP2 |
re |
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CI |
2.1469 |
2.1487 |
| CH |
1.0832 |
1.0791 |
| CF |
1.3496 |
1.3453 |
| CCl |
1.7540 |
1.7580 |
| HCI |
107.09 |
107.28 |
| ICF |
109.45 |
109.52 |
| ICCl |
112.23 |
112.10 |
| HCF |
109.65 |
109.74 |
| HCCl |
108.63 |
108.56 |
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FCCl |
109.73 |
109.59 |
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[1] A.Cuisset, J.R.Aviles Moreno, T.R.Huet, D.Petitprez, J.Demaison, and J.Crassous, J.Phys.Chem. A, 109,5708(2005).
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P.Soulard,
P.Asselin, A.Cuisset, J.R.Aviles Moreno, T.R.Huet, D.Petitprez,
J.Demaison, T.B.Freedman, X.Cao, L.A.Nafie, and J.Crassous,
Phys.Chem.Chem.Phys., 8,579(2006). |
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CH3I |
CH2ICl |
CH2I2 |
CH3CH2I |
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Table of Contents |
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Molecules/Iodine |
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Molecules/Chlorine |
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CHFClI.html |
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Last
Modified 3 Jan 2009 |
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